JP2007518561A - Method for recovering catalytic activity of spent hydroprocessing catalyst, spent hydroprocessing catalyst having recovered catalytic activity, and hydroprocessing method - Google Patents

Abstract

  Disclosed is a method for restoring the catalytic activity of a spent hydroprocessing catalyst because it has been used or because carbon has been deposited. The method includes a carbon reduction step in which the carbon is removed from the spent hydroprocessing catalyst in a controlled manner such that the carbon falls within a specifically defined concentration range. After the carbon removal step, the resulting catalyst having a reduced carbon concentration is contacted with the chelating agent, resulting in benefits from a controlled carbon reduction step. It is aged for the time necessary to make it chelated. In a preferred embodiment, the catalyst obtained from the chelation process is subjected to a sulfurization process that includes incorporating elemental sulfur therein and contacting the olefin with the catalyst.

Description

  The present invention relates to a method for recovering the catalytic activity of a spent hydrotreating catalyst, the resulting hydrotreating catalyst and its use in a hydrotreating method.

  WO 01/02092 discloses a process for regenerating a spent additive-based catalyst. This regeneration step is carried out by contacting the spent additive-based catalyst with oxygen at a temperature not exceeding 500 ° C. The resulting regenerated catalyst more preferably has a carbon content of less than 1% by weight before being subjected to an activation step by being contacted with an organic additive. This publication method is limited to additive-based catalysts, and this publication requires the carbon concentration on the regenerated catalyst to be adjusted within a certain range in order to benefit better from activation. Not aware that there is. Indeed, this publication suggests that it is best that the carbon content of the regenerated catalyst be as low as possible before it is subjected to an activation treatment. This publication does not disclose that in the catalyst activation step, the organic additive must remain on the catalyst during the aging period before drying.

  European Patent Application No. 0541994A1 adjusts the oxidative combustion of coke in order to adjust the residual coke content within the range of 0.5 to 10.0% by weight without reducing it to less than 0.5% by weight. Thus, a method for regenerating a hydrogenation catalyst comprising a support, a Group VI metal and a Group VIII metal on which coke is deposited is disclosed. This publication specifically mentions that if the oxidation conditions are too severe, the pore structure, surface area, and active sites of the catalyst can be altered to the worse. This publication does not show experimental data comparing the activity of the regenerated catalyst with the activity of the new catalyst, but only shows comparative data of certain physical properties of the two catalysts. In addition, nothing is disclosed regarding the reactivation of a spent catalyst using a chelating agent and the relationship between carbon removal and chelation.

  US Pat. No. 6,239066 B1 discloses a method for improving the activity of a catalyst by treatment with a chelating agent. It is also stated that this treatment method can also be used to improve the activity of the spent catalyst. The exemplary data presented in the examples shows that spent catalyst that has been regenerated and then treated with ethylenediaminetetraacetic acid (EDTA) has better relative volume activity (RVA) than spent catalyst that has only been regenerated. It shows that it is improved. There is no description of the carbon concentration on the spent catalyst, or regenerated catalyst, or regenerated and treated catalyst.

  In particular, where the catalyst is a spent high activity hydrotreating catalyst, there continues to be a need to find a better way to restore the activity of a catalyst that has lost activity through use.

  Accordingly, in one method of the invention, a spent hydroprocessing catalyst having a first carbon concentration greater than about 3% by weight is provided. The carbon concentration on the spent hydroprocessing catalyst is reduced, thereby having a carbon-reduced spent catalyst having a second carbon concentration in the range of about 0.5 wt% to about 2.5 wt%. Bring. Reducing the carbon concentration on the spent hydrotreating catalyst can be achieved by contacting the spent hydrotreating catalyst with a gas containing oxygen and removing it from the spent hydrotreating catalyst under conditions where the carbon burns. By adjusting the amount of carbon produced to provide a carbon-reduced spent catalyst having a second carbon concentration. The carbon-reduced spent catalyst is then treated with a chelator to provide a reactivated catalyst.

  According to another inventive method, the catalytic activity of a spent high activity hydroprocessing catalyst having reduced RVA and deposited carbon concentration is restored to a maximized regenerated RVA. The method includes providing a spent high activity hydrotreating catalyst having a reduced RVA and a deposited carbon concentration. A spent high activity hydroprocessing catalyst is obtained by using a high activity hydroprocessing catalyst under hydroprocessing conditions on which carbon is deposited, resulting in a deposited carbon concentration. A spent high activity hydrotreating catalyst is heat treated by contact with a gas containing oxygen under conditions where the carbon burns, thereby having a reduced carbon concentration and heat treated spent high activity hydroprocessing A treatment catalyst is produced. The reduced carbon concentration is adjusted to provide a heat treated spent high activity hydrotreating catalyst with maximized regeneration RVA by controlling the carbon combustion conditions.

  According to yet another invention, there is provided a catalyst comprising a spent hydroprocessing catalyst having recovered activity and having a deactivating concentration of carbon deposited thereon, wherein the deactivating concentration of carbon is provided. A portion of the carbon is removed by heat treating the spent hydrotreating catalyst in the presence of an oxygen-containing gas, resulting in an optimized concentration of carbon, which is then used in the heat treated spent hydrogen. The chemical conversion catalyst has already been chelated.

  A hydroprocessing method comprising a catalyst having recovered activity and a catalyst produced by the foregoing method comprising contacting a hydroprocessing catalyst reactivated under hydroprocessing conditions with a hydrocarbon feedstock. Can be used.

  Other objects and advantages of the invention will be apparent from the following detailed description and the appended claims.

  The present invention relates to a method for recovering the catalytic activity of a hydroprocessing catalyst that has been used due to use. The present invention further relates to a method for maximizing the amount of recovered catalytic activity of a spent hydroprocessing catalyst. The present invention also relates to a reactivated hydroprocessing catalyst and other catalyst compositions produced by processing a spent hydroprocessing catalyst using the inventive method described herein. Related to things. Furthermore, the present invention relates to a hydroprocessing method utilizing the reactivated hydroprocessing catalyst and other spent catalyst having the recovered catalytic activity of the present invention.

  The hydrotreating catalyst of the present invention can be any suitable hydrotreating catalyst, including conventional hydrotreating catalysts that include a metal component on a support material. The metal component can include a Group VIB metal component or a Group VIII metal component, or both metal components. The hydrotreating catalyst preferably includes both a Group VIB metal component and a Group VIII metal component. The hydrotreating catalyst can also contain a promoter such as a phosphorus component.

  The Group VIII metal component of the hydroprocessing catalyst composition is a Group VIII metal or metal compound that, together with the other components of the catalyst composition, suitably provides a hydroprocessing catalyst. The Group VIII metal can be selected from the group consisting of nickel, cobalt, palladium and platinum. Preferably, the Group VIII metal is nickel or cobalt, and most preferably, the Group VIII metal is cobalt.

  The Group VIII metal component contained in the hydrotreating catalyst composition can be in the form of an element or in the form of a metal compound such as, for example, an oxide or sulfide. The amount of Group VIII metal in the hydroprocessing catalyst composition can range from about 0.1 to about 6% by weight of metal elements, based on the total weight of the hydroprocessing catalyst composition. Preferably, the concentration of Group VIII metal in the hydrotreating catalyst composition is in the range of 0.3 wt% to 5 wt%, and most preferably the concentration is in the range of 0.5 wt% to 4 wt%. It is in.

  The Group VIB metal component of the hydroprocessing catalyst composition is a Group VIB metal or metal compound that, together with the other components of the hydroprocessing catalyst composition, suitably provides a hydroprocessing catalyst. The group VIB metal can be selected from the group consisting of chromium, molybdenum and tungsten. The preferred group VIB metal is molybdenum or chromium, and most preferably the group VIB metal is molybdenum.

  The group VIB metal component contained in the hydrotreating catalyst composition may be in the form of an element or in the form of a metal compound such as an oxide or sulfide. The amount of Group VIB metal in the hydroprocessing catalyst composition can range from about 5 to about 25 weight percent metal elements, based on the total weight of the hydroprocessing catalyst composition. Preferably, the concentration of the Group VIB metal in the hydrotreating catalyst composition is in the range of 6 wt% to 22 wt%, and most preferably the concentration is in the range of 7 wt% to 20 wt%.

  The support material for the hydroprocessing catalyst can be any material that suitably provides a support for supporting the metal hydroprocessing component of the hydroprocessing catalyst, and includes a porous refractory oxide. Examples of possible suitable porous refractory oxides include silica, magnesia, silica-titania, zirconia, silica-zirconia, titania, titania-alumina, zirconia-alumina, silica-titania, alumina, silica-alumina. , And aluminosilicates. The alumina can take a variety of forms, for example, α-alumina, β-alumina, γ-alumina, δ-alumina, η-alumina, θ-alumina, boehmite, or mixtures thereof. A preferred porous refractory oxide is amorphous alumina. Of the available amorphous aluminas, γ-alumina is most preferred.

The porous refractory oxide generally has an average pore size in the range of about 50 to about 200, preferably 70 to 175, and most preferably 80 to 150. The total pore volume of the porous refractory oxide measured by standard mercury porosimetry is in the range of about 0.2 cc / g to about 2 cc / g. Preferably the pore volume is in the range of 0.3 cc / g to 1.5 cc / g, most preferably in the range of 0.4 cc / g to 1 cc / g. B. E. T.A. The surface area of the porous refractory oxide measured by the method is generally greater than about 100 m ² / g, typically in the range of about 100 to about 400 m ² / g.

  One of the methods of the present invention is specifically directed to the treatment of a highly active hydrotreating process that has become a spent catalyst, typically because it has been used or because carbon has been deposited thereon, or both. Therefore, a part of the lost catalyst activity is recovered. This spent high activity hydrotreating catalyst can have RVA reduced to below the relative volume activity (RVA) when in the new state and can have a certain concentration of deposited carbon.

As used herein, the term “relative volume activity” (RVA) refers to the hydrodesulfurization (HDS) or hydrodesulfurization of a used new catalyst in a new unused state relative to the catalytic activity of the same specified catalyst. Refers to catalytic activity with respect to nitrogen (HDN). Therefore, the RVA of the new, unused reference catalyst is 1 by definition. The RVA of the evaluated catalyst is represented by the following formula:
RVA = (rate constant of evaluated catalyst) / (rate constant of new reference catalyst)
For hydrodesulfurization (HDS) RVA, the rate constant is calculated assuming an HDS reaction order of 1.3; for hydrodenitrogenation (HDN) RVA, the rate constant is 1. Calculated assuming an HDN reaction order of zero.

  High activity hydrotreating catalysts are sulfur treated hydrotreating catalysts containing porous refractory oxides and metal hydrotreating components and are prepared by special methods that provide high activity and other desirable properties. A highly active hydrotreating catalyst is prepared by first combining a porous refractory oxide support material and at least one metal hydrogenation component, including a volatile compound, thereby providing a catalyst precursor. can do. Volatile compounds are compounds used in the formation of catalyst precursors, from water, organic solvents such as aliphatic and aromatic hydrocarbons, alcohols, ketones, organic ligands and any combination thereof. Generally selected from the group consisting of Thus, the catalyst precursor can include a porous refractory oxide support material, a metal hydrogenation component, and a concentration of volatile compounds. This catalyst precursor is then subjected to a sulfur treatment step to incorporate sulfur (either elemental sulfur or a sulfur compound, or a combination of both) into the catalyst precursor, thereby providing a sulfur treated catalyst precursor. Bring. The sulfur treatment step used to provide the sulfur treated catalyst precursor reduces the concentration of volatile compounds present in the catalyst precursor simultaneously with or subsequent to the sulfur treatment, resulting in a highly active hydrotreatment catalyst. Can bring.

  The porous oxide support material and the metal hydrogenation component of the catalyst precursor are combined using any suitable, known, method for combining such catalyst components, impregnation, Methods such as co-mixing and co-precipitation can be included. However, a porous refractory oxide support material is first formed into particles, such as extrudates, pills and other agglomerated particles, and the metal hydride component is known incipient wetness. It is preferably incorporated into the particles by a wetness) impregnation method.

  The metal impregnation solution used to incorporate the metal compound or metal compounds into the porous refractory oxide support can be a source of volatile compounds, and as described above, water or alcohol compounds Or an organic solvent or a combination thereof. The metal impregnation solution is preferably an aqueous solution of a metal compound. Metal compounds suitable for use in forming the metal impregnation solution are those compounds that can be dissolved in the particular solvent used to form the impregnation solution and converted to metal sulfide by further processing.

  Group VIII metal compounds that can be used in the metal impregnation solution include, for example, Group VIII metal carbonates, Group VIII metal nitrates, Group VIII metal sulfates, Group VIII metal thiocyanates, Group VIII Metal oxides and mixtures of any two or more of these may be included.

  Group VIB metal compounds that can be used in the metal impregnation solution include, for example, group VIB metal oxides, group VIB metal sulfides, group VIB carbonyl compounds, group VIB acetate compounds, and VIB in solution. Group elemental metals and mixtures of any two or more of these may be included. For the preferred Group VIB metal compounds of molybdenum, molybdates and phosphomolybdates can be used.

  The concentration of the metal compound in the metal impregnation solution is selected to achieve the desired metal concentration in the final catalyst composition. Usually, the concentration of the metal compound in the impregnation solution is in the range of 0.01 to 100 moles per liter of solution.

  The catalyst precursor that is to undergo further sulfur treatment steps should have a concentration of volatile compounds that does not fall below 0.5 wt%, based on the total weight of the catalyst precursor, The amount of volatile compounds in the precursor should be in the range of 0.5% to 25% by weight. The preferred concentration of volatile compounds in the catalyst precursor is in the range of 2% to 25% by weight, and most preferably in the range of 4% to 10% by weight.

  Prior to the sulfur treatment, the catalyst precursor can optionally be dried to adjust the concentration of volatile compounds in the catalyst precursor within the aforementioned range, but the calcining temperature prior to the sulfur treatment step. Don't be subject to conditions. Thus, the catalyst precursor is not calcined prior to incorporating sulfur or sulfur compounds therein. The calcination temperature condition is 400 ° C. or a temperature exceeding 400 ° C., and is usually in the range of 400 ° C. to 600 ° C. Thus, the catalyst precursor may be exposed to temperatures below 400 ° C. prior to the sulfidation step. However, with the condition that the temperature conditions are not such that the resulting concentration of the volatile compounds in the resulting catalyst precursor is in the desired concentration range as mentioned above. is there. Typically, the catalyst precursor can be dried in the presence of air at a drying temperature ranging from ambient temperature to 400 ° C, but more typically from 30 ° C to 250 ° C.

  A catalyst precursor having a concentration of volatile compounds within the range as described above is subjected to a sulfur treatment step, whereby sulfur or sulfur compounds are incorporated into the catalyst precursor, thereby resulting in a highly active hydrotreatment catalyst. . Any suitable method known to those skilled in the art can be used to produce a highly active hydroprocessing catalyst by treating the catalyst precursor with sulfur or a sulfur compound, for example, In-situ and ex-situ sulfidation and sulfidation methods. As used herein, terms such as sulfur treatment or sulfur treatment or sulfur treatment or other like terms are used to describe such methods in-situ (ie, within the process reactor region) or ex A method comprising a combination of both sulfidation and sulfidation methods and sulfidation and sulfidation, whether carried out by any combination of in-situ (ie outside the process reactor region) or in-situ or ex-situ treatment method Is intended to encompass.

  In a typical in-situ sulfidation process, the catalyst precursor is placed in a reaction vessel that defines a reaction zone. The fluid stream containing the sulfur compound is passed over the catalyst precursor and contacted with the catalyst precursor under temperature conditions suitable to provide a sulfidation catalyst, and thus a highly active hydroprocessing catalyst. Sulfur compounds include hydrogen sulfide, organic sulfur compounds normally present in petroleum hydrocarbon feedstocks, and other organic sulfur compounds (eg, dimethyl sulfide, dimethyl disulfide, dimethyl sulfoxide, dimethyl mercaptan, butyl mercaptan, and carbon disulfide). Any known suitable sulfiding agent such as Typical temperatures at which the sulfided fluid stream is contacted with the catalyst precursor are in the range of 150 ° C to 400 ° C, and more typically 200 ° C to 350 ° C.

  In the ex-situ sulfidation process, the catalyst precursor is sulfidized before being charged to the reaction vessel. The ex-situ sulfidation process can be performed, for example, by contacting the catalyst precursor with a sulfiding agent, as described above, or with a hydrogen sulfide-containing fluid under high temperature conditions, followed by an optional passivation step. Any number of suitable sulfidation methods can be included.

  A preferred sulfurization step is to contact the catalyst precursor with elemental sulfur under conditions in which sulfur is incorporated into the pores of the catalyst precursor by sublimation, by melting, or a combination of both, so that the sulfur is the catalyst precursor. Realize what is incorporated in. A suitable sulfurization method for incorporating this sulfur is described in detail in US Pat. No. 5,468,372, incorporated herein by reference.

  There are two general methods for carrying out the sulfurization of the catalyst precursor with elemental sulfur. A first preferred method involves contacting the catalyst precursor with elemental sulfur at a temperature at which elemental sulfur is substantially incorporated into the pores of the catalyst precursor by sublimation and / or melting, and subsequently Heating the sulfur-incorporated catalyst precursor in the presence of a liquid olefinic hydrocarbon at a temperature above about 150 ° C.

  The second method involves contacting the catalyst precursor with a mixture of powdered elemental sulfur and liquid olefinic hydrocarbon and the resulting mixture of olefin, sulfur and catalyst precursor at about 150 ° C. Heating to a higher temperature. In this procedure, the heating rate is slow enough so that sulfur is introduced into the pores of the catalyst precursor by sublimation and / or melting before the olefin reacts and reaches a temperature that increases the resistance of the sulfur to stripping removal. is doing.

  In the preferred sulfidation process, the catalyst precursor is first contacted with elemental sulfur at a temperature at which sulfur is incorporated into the precursor by sublimation and / or melting. The catalyst precursor can be contacted with the molten sulfur, but first the catalyst precursor is mixed with the powdered elemental sulfur, and then the resulting mixture of sulfur and catalyst precursor is mixed with sulfur. Heating to a temperature higher than the sublimation temperature is preferred.

  Generally, the catalyst precursor is heated in the presence of powdered elemental sulfur at a temperature above about 80 ° C. Preferably, the sulfur impregnation step will be performed at a temperature ranging from about 90 ° C. to about 130 ° C. or higher, for example, the boiling point of sulfur of about 445 ° C. The catalyst precursor and sulfur are preferably heated together at a temperature in the range of about 105 ° C to about 125 ° C. Typically, the catalyst precursor and powdered sulfur are placed in an oscillating or rotary mixer and heated to the desired temperature for a time sufficient to allow the sulfur to be incorporated into the pores of the catalyst precursor. The heating time is usually in the range of about 0.1 hours to about 10 hours or more.

  The amount of sulfur used depends on the amount of catalyst metal present in the catalyst precursor that must be converted to sulfide. Usually, the amount of sulfur used is calculated based on the stoichiometric amount of sulfur required to convert all of the metal present in the catalyst precursor to the sulfide form. For example, a catalyst precursor containing molybdenum requires 2 mol of sulfur each time 1 mol of molybdenum is converted to molybdenum disulfide, and the same calculation is performed for other metals.

  The catalyst precursor incorporating sulfur is then contacted with the liquid olefin over time at the elevated temperature at which the olefin reacts, resulting in a highly active hydroprocessing catalyst. Typically, the contact temperature is greater than about 150 ° C, more typically the contact temperature is in the range of about 150 ° C to about 350 ° C, preferably about 200 ° C to about 325 ° C. Contact time will depend on the temperature and vapor pressure of the olefin, the higher the temperature and the higher the vapor pressure, the shorter the required time. Generally, the contact time is in the range of about 0.1 hours to about 10 hours.

  It is important that the olefin is a liquid at high contact temperatures. The olefin is preferably a higher olefin, i.e. an olefin having a carbon number of greater than 6, preferably greater than 8.

  In one preferred sulfurization process embodiment, the catalyst precursor is contacted simultaneously with both elemental sulfur, preferably in powder form, and the olefinic hydrocarbon. According to this method, a mixture of powdered elemental sulfur and an olefinic hydrocarbon solvent is first produced. An oil to sulfur weight ratio in the range of about 1: 1 to about 4: 1 is suitable, with about 2: 1 being a preferred ratio. The mixture can be heated to facilitate uniform mixing of the components, particularly when the olefinic hydrocarbon is not liquid at ambient conditions. Toluene or other light hydrocarbon solvents can be added to reduce the viscosity of the mixture. Moreover, the same effect will be achieved by increasing heating. The mixture of olefin and sulfur is then added to the pre-weighed catalyst precursor and mixed therewith. The catalyst precursor, a mixture of olefin and sulfur, is then heated to an olefin reaction temperature of greater than about 150 ° C. Preferably, this temperature is in the range of about 150 ° C to about 350 ° C, more preferably about 200 ° C to about 325 ° C. The heating time is in the range of about 0.1 to about 10 hours.

  The sulfurized catalyst precursor can also be further treated with sulfur by performing sulfidation in-situ or ex-situ or a combination thereof.

  An important aspect of the method of the present invention is the high activity hydroprocessing that has been lost as a result of using a hydroprocessing catalyst, such as use under hydroprocessing conditions, or as a result of carbon deposition thereon. The object is to recover the catalytic activity of the hydrotreating catalyst including the catalyst. It is understood that the term hydrotreating catalyst used herein is broadly defined to include a highly active hydrotreating catalyst, as described in detail above. Accordingly, when referring to hydroprocessing catalysts herein, highly active hydroprocessing catalysts are also included and encompassed. It will be appreciated that the inventive methods described herein are particularly applicable to the processing of highly active hydroprocessing catalysts due to their unique and unique properties.

  The hydrotreating catalyst can be used for hydrotreating hydrocarbon feedstocks under suitable hydrotreating process conditions. Typical hydrocarbon feedstocks are oil-derived oils such as atmospheric distillate, vacuum distillate, cracking distillate, raffinate, hydrotreated oil, history oil, and hydrotreated. All other possible hydrocarbons can be included. More typically, the hydrocarbon feedstock treated with the hydrotreating catalyst is a petroleum distillate, such as a direct distillate or cracking distillate, and the hydrotreating is from a hydrocarbon feedstock. Removing sulfur from sulfur-containing compounds, nitrogen from nitrogen-containing compounds, or both.

  More specifically, the hydrocarbon feedstock is, for example, naphtha (usually containing hydrocarbons boiling in the range of 100 ° C. (212 ° F.) to 160 ° C. (320 ° F.)), kerosene (usually 150 Boiling oil in the range of 230 ° C (446 ° F) to 350 ° C (662 ° F), containing hydrocarbons boiling in the range of 0 ° C (302 ° F) to 230 ° C (446 ° F) Including hydrocarbons) and even heavy gas oils containing hydrocarbons boiling in the range of 350 ° C. (662 ° F.) to 430 ° C. (806 ° F.).

  The hydrotreating conditions to which the hydrotreating catalyst is exposed are not critical, such as the type of hydrocarbon feed being treated and the amount of sulfur and nitrogen contaminants contained in the hydrocarbon feed. In consideration of the above factors, it is selected as necessary. Generally, the hydrocarbon feedstock is typically from about 150 ° C. (302 ° F.) to about 538 ° C. (1000 ° F.), preferably from 200 ° C. (392 ° F.) to about 450 ° C. (842 ° F.), most preferably Is contacted with the hydrotreating catalyst in the presence of hydrogen under hydrotreating conditions such as hydrotreating contact temperature ranging from 250 ° C. (482 ° F.) to 425 ° C. (797 ° F.).

The hydroprocessing total contact pressure is generally in the range of about 500 psia to about 6000 psia, the hydrogen partial pressure in the range of about 500 psia to about 3000 psia, the volume of hydrocarbon feedstock in the range of about 500 SCFB to about 10,000 SCFB. Per hydrogenation rate, and a time-based hydroprocessing fluid space velocity (LHSV) in the range of about 0.2 hr ⁻¹ to 5 hr ⁻¹ . Preferred total hydroprocessing contact pressures are in the range of 500 psia to 2500 psia, most preferably in the range of 500 psia to 2000 psia, with preferred hydrogen partial pressures of 800 psia to 2000 psia, most preferably 1000 psia to 1800 psia. LHSV is preferably, ^4hr from 0.2 hr ^{-1 -1,} and most preferably, from 0.2 in the range of ^{3 hr -1.} The hydrogenation rate is preferably in the range of 600 SCFB to 8000 SCFB, more preferably 700 SCFB to 6000 SCFB.

  The spent hydroprocessing catalyst has a catalytic activity that is lower than that of the catalyst in the new state, as reflected by a relative volume activity (RVA) of less than 1. In general, hydrotreating catalysts are considered used when the RVA is less than 0.65, but from economic and process considerations it is usually determined when the catalyst is considered used. Thus, the RVA of the spent hydroprocessing catalyst can be less than 0.5 and even less than 0.4.

  The hydrotreating catalyst can be used by being used under hydrotreating conditions as described above. One cause of losing catalytic activity is that carbon-containing material accumulates in the pore structure of the hydroprocessing catalyst as a result of its use, and the spent hydroprocessing catalyst is typically greater than 3% by weight. It is generally believed that it can have a carbon content and is based on the total weight of the spent hydroprocessing catalyst including carbon and other components deposited on the hydroprocessing catalyst. Here, the wt% typically has a carbon content of the spent hydroprocessing catalyst in the range of 5 wt% to 25 wt%, and more typically the carbon content is 6 wt% to 20 wt%. It is in the range of weight percent.

  An important feature of the process of the present invention for maximizing the recovery of the catalytic activity of the spent hydroprocessing catalyst is that the first step of carbon reduction results in a controlled concentration of carbon on the spent hydroprocessing catalyst. When the spent hydrotreating catalyst is subsequently treated with a chelating agent in accordance with the present invention, a reactivated catalyst having the desired recovered catalytic activity is provided. .

  It was unexpectedly discovered that there is an optimal amount of carbon that must remain on the spent hydroprocessing catalyst after the carbon reduction step to get the best benefit from treatment with a chelating agent. . In order to provide the best improvement in restoring catalyst activity through chelation, the spent hydrotreating catalyst first reduces the carbon content to a concentration level no less than about 0.5 wt%. And thereby a carbon-reducing catalyst should be realized, and in general the carbon concentration of the carbon-reducing catalyst should be in the range of 0.5% to 2.5% by weight. In order to provide a large amount of recovered catalytic activity after chelation, the carbon concentration on the carbon reducing catalyst should be in the range of 0.75 wt% to 2 wt%, preferably the carbon concentration is The range is from 1% by weight to 1.75% by weight.

  If the carbon concentration of the carbon-reducing catalyst is adjusted within the concentration range required according to the method of the present invention, the catalyst activity is used in such a way that the optimum or maximum level of recovered catalyst activity is obtained. It is possible to recover from spent hydroprocessing. This maximized regeneration RVA exceeds, and preferably substantially exceeds, the reduced RVA of the spent hydroprocessing catalyst. Thus, in general, the maximized regeneration RVA of the carbon reduction catalyst can exceed 0.65. However, it is most desirable for the maximized regeneration RVA to be as high as possible, so the RVA can exceed 0.7 and even 0.75. In most cases, the practical upper limit for maximized regeneration RVA is 0.9.

  Although any suitable method known in the art can be used to reduce the carbon concentration on the spent hydroprocessing catalyst and thereby achieve a carbon-reducing catalyst, the preferred method is Heat treating the spent hydrotreating catalyst under appropriate carbon combustion conditions and in a controlled manner by contacting it with an oxygen-containing gas containing oxygen to remove the carbon present on the spent hydrotreating catalyst. Combustion, or incineration, or oxidation to achieve a carbon-reduced catalyst having a reduced carbon concentration that is less than the carbon concentration on the spent hydroprocessing catalyst.

  The fact that the recovered catalyst activity is maximized when the carbon concentration on the carbon reduction catalyst is adjusted within a certain range as described above and the carbon reduction catalyst is subsequently treated with a chelating agent is It is a particularly important aspect of the inventive method.

  The required carbon combustion conditions may depend on the amount of carbon on the spent hydroprocessing catalyst and the desired carbon concentration on the carbon reduction catalyst. In general, the spent hydrotreating catalyst is contacted with an oxygen-containing gas under conditions where the spent hydrotreating catalyst temperature does not exceed 500 ° C., and a suitable heat treatment or carbon combustion temperature is about It is in the range of 300 ° C to about 500 ° C. Preferred carbon combustion temperatures are in the range of 320 ° C to 475 ° C, most preferably 350 ° C to 425 ° C.

  The oxygen concentration of the oxygen-containing gas can be adjusted to provide the desired carbon combustion temperature conditions. The oxygen-containing gas is preferably air, and can be diluted with another gas, for example, an inert gas such as nitrogen, to adjust the oxygen concentration in the oxygen-containing gas. Carbon combustion can be performed in a combustion zone where a spent hydroprocessing catalyst is placed and an oxygen-containing gas is introduced. The length of time to perform carbon combustion is not critical and is the length that results in a carbon-reducing catalyst having the desired carbon concentration, generally about 0.1 to 48 hours, or More than that.

  A carbon reducing catalyst having a specifically defined carbon concentration results in a reactivated catalyst that has been treated with a chelating agent, thereby having recovered catalytic activity. One suitable chelation method is described in detail in US Pat. No. 6,291,394, which is incorporated herein by reference. In a preferred process, the carbon reducing catalyst is contacted with a chelating agent, preferably dissolved in a liquid carrier, in a manner that ensures that the chelating agent is fully incorporated into the carbon reducing catalyst, Or get wet. This contact is then followed by an aging period, during which time the chelator can remain on the carbon-reducing catalyst, resulting in an aging catalyst. This aged catalyst is then subjected to a heat treatment that can include drying or calcining, or both, followed by sulfur treatment, resulting in a catalyst having recovered catalytic activity.

  Chelating agents, or chelants, suitable for use in the chelating step of the method of the present invention are derived from any of the metal components contained in the carbon reducing catalyst, such as any of Group VIII metals and Group VIB metals. Includes compounds capable of forming complexes. It is particularly important for the process of the present invention that the kerant has the property of bringing about recovery of catalytic activity in the carbon reduction catalyst.

  While not intending to be bound by any particular theory, the chelating agent is nevertheless included in the carbon-reducing catalyst and is subject to previous use and exposure to the carbon combustion conditions of the hydrotreating catalyst. In addition, it is considered that the recovery of the catalytic activity is brought about by redispersing the active metal aggregated by exposure to high temperature and the derivative from which the carbon-reducing catalyst is derived. The amount of metal redispersion can be verified and observed by electron micrographs.

  The chelating agent is added to the carbon reducing catalyst in a liquid state, preferably by using a solution containing a chelating agent that forms a complex with the aggregated metal of the carbon reducing catalyst. Thus, the complex is present in the liquid phase that provides the mobility of the complex and assists in the movement of the metal throughout the carbon-reducing catalyst, thereby realizing the redispersion of the metal.

  Any keyant compound that adequately provides the benefit of the recovered catalytic activity required by the inventive methods described herein can be used in chelating carbon-reduced catalysts. Among these chelant compounds are chelating agents that contain at least one nitrogen atom that can serve as an electron donor atom to form a complex with the metal of the carbon-reducing catalyst.

  Examples of possible chelating agents containing nitrogen atoms include compounds that can be classified as aminocarboxylic acids, polyamines, aminoalcohols, oximes, and polyethyleneimines.

  Examples of aminocarboxylic acids include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (NTA).

  Examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetraamine, and triaminotriethylamine.

  Examples of amino alcohols include triethanolamine (TEA) and N-hydroxyethylethylenediamine.

  A preferred chelating agent for use in the method of the present invention is an aminocarboxylic acid which can be represented by the following formula:

式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５は、１０個までの炭素原子を有するアルキル、アルケニルおよびアリルから、それぞれ独立に選択され、カルボニル、カルボキシル、エステル、エーテル、アミノ、またはアミドから選択された１種以上の基により置換されていてもよく、Ｒ_６およびＲ_７は１０個までの炭素原子を有するアルキレン基から、それぞれ独立に選択され、ｎは０または１であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５の１種以上は、次式を有する。

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from alkyl, alkenyl and allyl having up to 10 carbon atoms, and are carbonyl, carboxyl, ester, ether, amino, Or optionally substituted by one or more groups selected from amides, wherein R ₆ and R ₇ are each independently selected from alkylene groups having up to 10 carbon atoms, and n is 0 or 1 , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the following formula:

式中、Ｒ_８は、１から４個の炭素原子を有するアルキレンであり、Ｘは水素または別のカチオンである。

Where R ₈ is alkylene having 1 to 4 carbon atoms and X is hydrogen or another cation.

  Preferred chelating agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA). The most preferred chelating agent is DTPA.

  In any suitable means or method, the carbon reducing catalyst can be used to contact a chelating agent or a solution containing a concentration of chelating agent. However, it is assumed that such a means or method can properly incorporate or impregnate the chelating agent in the pores of the carbon-reducing catalyst. Examples of suitable methods for applying the chelating agent or chelating solution to the carbon reducing catalyst include dipping or spraying. The preferred method for contacting the carbon reducing catalyst with the chelating agent or chelating solution is any suitable impregnation method known to those skilled in the art, for example, impregnation by the incipient wetness method, The amount or volume of chelate solution added is such that the total volume of chelate solution added falls in the range up to approximately the total pore volume of the carbon reducing catalyst to be impregnated by the chelate solution.

  The chelating solution can be a solution comprising a chelating agent and a solvent that properly dissolves the chelating agent. Possible solvents are water and alcohols such as methanol and ethanol, for example, and the preferred solvent for the chelating agent is water. The amount of chelating agent applied to the carbon reducing catalyst must provide the desired recovered catalytic activity, as described herein, and generally the amount is in the carbon reducing catalyst. The amount of active metal present, i.e., a chelating agent in the range of about 0.005 mole keyant to about 1 mole keyant per mole of Group VIII and VIB metals described above, is incorporated into the carbon-reducing catalyst. It is more preferred to add to the carbon reducing catalyst an amount of chelating agent that is present in the range of 0.01 to 0.5 moles of chelating agent added per mole of hydrogenated metal in the carbon reducing catalyst. Most preferably, the amount of chelating agent added to the carbon reduction catalyst is such that the added kerant is in the range of 0.05 to 0.1 moles per mole of metal hydride.

  An important aspect of the present invention treats a spent hydrotreatment catalyst by combining a carbon removal step and a chelator treatment step that result in residual carbon concentration on the carbon reduction catalyst, adjusted within a well defined range. It is understood that a reactivated catalyst can be provided that has a higher level of recovery catalytic activity than that achieved using an alternative method. In addition, to realize the benefits from the combined step of removing a controlled amount of carbon from the spent hydrotreating catalyst and subsequently chelating the resulting carbon-reduced catalyst. In addition, it has been discovered that the chelator treatment step is essential to include a sufficiently long aging or soaking of the carbon-reducing catalyst. If this time is not long enough, there will be no visible benefit.

  A carbon-reducing catalyst incorporating a chelating agent is therefore aged over the aging time necessary to enhance the recovered catalytic activity. It is theorized that a sufficiently long aging period is necessary for the keelant to react with the carbon-reducing catalyst metal, thereby forming a chelate and redispersing the metal. In any case, there is a minimum amount of time required for the aging period before a greatly increased benefit appears in the recovered catalytic activity of the carbon-reduced catalyst treated with the kerant. This minimum aging time may depend on the temperature at which aging is carried out and the type and amount of keelant used for the carbon reduction catalyst.

  In general, in order for a preferred aminocarboxylic acid chelator to benefit greatly from aging, it is important that the aging time exceeds about 10 hours, although it is not essential, Preferably the aging period should exceed 20 hours, and most preferably 40 hours. There is also a ripening time maximum at which the recovered catalytic activity does not increase significantly. The maximum aging time generally does not exceed 1200 hours. The preferred maximum aging time is less than 1000 hours, more preferably the maximum aging time is less than 750 hours. Thus, the aging period for contacting the carbon reducing catalyst or the aging period for the chelating agent incorporated in the pores of the carbon reducing catalyst to remain on the catalyst or soak can be about 10 hours. From about 1200 hours, preferably from 20 hours to 1000 hours, most preferably from 40 hours to 750 hours.

  The aging temperature at which aging is performed can be any temperature that results in an aging catalyst in which the metal of the carbon-reducing catalyst is at least somewhat redispersed, generally from about ambient temperature, such as from about 10 ° C to about 10 ° C. It can be in the range of 37 ° C, about 50 ° C or 60 ° C.

  The aging catalyst is then subjected to a heat treatment that may include drying or calcination, or both. However, the aging catalyst is preferably not exposed to calcination conditions. Drying the aging catalyst is removing at least a portion of the chelating solution solvent from the aging catalyst while leaving at least a portion, preferably a majority, of the chelating agent on the aging catalyst. In a preferred embodiment of the present invention, if the dry aging catalyst undergoes a similar, if not identical, sulfur treatment to that described above for the preparation or production of a highly active hydrotreating catalyst, It is important to include a certain amount or concentration of keelant.

  In drying the aged catalyst, it is desirable to remove as little of the keyant as possible from the aged catalyst, and therefore, incorporated into the carbon-reduced catalyst, based on the total weight of the keyant incorporated into the carbon-reduced catalyst. More than about 50% by weight of the keand will remain in the resulting dry aging catalyst. When the dry aging catalyst undergoes sulfidation treatment, preferably the amount of keyant that remains on the dry aging catalyst is greater than 75% by weight, and most preferably greater than 90% by weight of the keyant initially added to the carbon reduction catalyst. Remains in the carbon-reducing catalyst. Accordingly, less than about 50% by weight of the keyrant initially added to the carbon reduction catalyst in the chelation process must be removed from the aged catalyst during the drying step. If desired, preferably less than 25 wt.%, And most preferably less than 10 wt.% Of the keyrant incorporated in the carbon reduction catalyst is removed from the aged catalyst.

  Drying can be performed by any suitable method known to those skilled in the art. Typically, hot air or any other suitable gas, such as nitrogen and carbon dioxide, is passed over the aged catalyst to dry the aged catalyst. The drying temperature should not exceed 200 ° C and is generally in the range of 90 ° C to 180 ° C. Preferably, the drying temperature is less than 175 ° C and ranges from 100 ° C to 175 ° C. The drying step is carefully controlled to avoid evaporation or conversion of the keyrant or chelate.

  In a preferred embodiment of the present invention, as discussed above, a dry aging catalyst containing a keyant or chelate remaining therein resulfurizes the metal hydride component present in the form of an oxide. In order to do so, it is treated with sulfur. The sulfur treatment of the dry aging catalyst is the same sulfur treatment method as described above with respect to the sulfur treatment of the catalyst precursor in the preparation or production of a highly active hydrotreating catalyst.

  The reactivation catalyst of the present invention should have a recovery catalyst activity such that the RVA is greater than 0.80, but more particularly, the RVA of the reactivation catalyst is greater than 0.85. It is preferred to maximize the amount of recovery activity of the spent hydroprocessing catalyst by the process of the present invention, and therefore the RVA of the reactivated catalyst is preferably greater than 0.90, and most preferably the RVA is less than 0.3. Over 95.

  The hydrotreating catalyst treated by the method described herein may be suitably used to hydrotreat a hydrocarbon feedstock under hydrotreating conditions fully described above. it can.

  The following examples are presented to illustrate the invention, but they should not be construed as limiting the scope of the invention.

  Example 1 includes an experiment used to reactivate and restore the catalytic activity of a commercial hydroprocessing catalyst that has been used by being used in the hydroprocessing of a distillate feedstock. The room method is described.

  A sample of used CENTINEL ™ DC-2118 high activity hydrotreating catalyst was obtained from a commercial user of the catalyst. CENTINEL ™ DC-2118 is a highly active hydroprocessing catalyst containing cobalt and molybdenum hydride metal components supported on an alumina support and is marketed by Criterion Catalysts & Technologies, Houston, TX. Yes. The carbon concentrations of individual samples A, B, C, D, E, F, G and H are shown in Table 2 below, respectively.

  Each sample was carbon burned by passing air over the sample at a temperature below 400 ° C. The combustion conditions were carefully controlled so that only a portion of the carbon on each sample was burned, leaving a residual amount of carbon on the resulting heat-treated spent or carbon-reduced catalyst. The carbon concentrations of the individual carbon-reduced catalyst samples A, B, C, D, E, F, G and H are shown in Table 2 below, respectively.

  Samples A, B, C, F, G and H were each treated with a chelating agent according to the present invention. Sample D was not treated with a chelating agent, and sample E was treated with a chelating agent, but aging according to the present invention was not performed.

  The chelate solution used to treat the carbon-reduced catalyst sample consisted of 1 (1) parts by weight DTPA, 0.11 parts by weight ammonium hydroxide, and 10 parts by weight water. Carbon-reduced catalyst samples were impregnated with a chelate solution by a standard incipient wetness method, and approximately 98% by volume of the available pore volume of the carbon-reduced catalyst was filled with the chelate solution. Each sample of impregnated carbon-reducing catalyst was then mixed well and allowed to age for 2 weeks at room temperature in a closed vessel to provide an aged catalyst.

  The aged catalyst sample was then dried in air at a temperature of about 150 ° C. for about 2 hours. This drying was performed so that the majority of the DTPA chelator remained on the resulting dried catalyst and the majority of the water was removed from the aged catalyst.

  The dried catalyst was then subjected to a sulfidation step. In order to sulfidize the dry catalyst, 13.5 parts by weight of elemental sulfur was added to 100 parts by weight of the dry catalyst and mixed. The mixture was then brought to a temperature of about 120 ° C. and maintained for a time sufficient to incorporate sulfur into the pores of the dry catalyst.

  After incorporating sulfur, an α-olefin blend containing an α-olefin having 14 to 30 carbon atoms was incorporated into the pores of the dried catalyst incorporating sulfur by an incipient wetness method. The amount of α-olefin added to the dry catalyst incorporating sulfur was sufficient to fill approximately 90% by volume of the available pore volume. The catalyst thus prepared was then subjected to a heat treatment, and the sample was heated in a stream of air at a temperature of about 260 ° C. for a time sufficient to provide a dry reactivated catalyst.

  Samples A, B, C, F, G, and H (ie, reactivated samples treated by the method of the present invention), respectively, sample D that was not treated with chelator and treated with chelator Sample E, which was not aged according to the present invention, was tested for catalytic activity by the procedure described in Example 2.

  In this Example 2, the laboratory used to test the catalytic activity of the reactivated catalyst sample described in Example 1 against the catalytic activity of the new CENTINEL ™ DC-2118 high activity hydrotreating catalyst. Describe the test procedure and feedstock.

Table 1 shows the properties of the feedstock used in conducting the activity test. To conduct the activity test, 50 cc of the catalyst sample in question was placed in a test reactor operating under hydroprocessing reaction conditions. The reaction conditions included a reaction temperature of about 355 ° C., a total pressure of 600 psia, a feed rate such that the time-based liquid space velocity was 1 hr ⁻¹ , a 1200 SCF / barrel hydrogen to oil ratio, and an operating time of 500 hours. Was included.

  The results of the activity test described in Example 2 are shown in Table 2, and FIG. 1 shows a graph of the results. As can be seen from the presentation of this result, especially when the carbon content is adjusted within a certain range prior to chelation, as evidenced by the presentation of the graph of FIG. Recovery of the catalytic activity of the spent hydroprocessing catalyst after treatment is maximized.

Reactivated hydrotreating prepared by the method of the present invention wherein the spent hydrotreating catalyst is first treated by removing some of the carbon on it and then treated by chelation. FIG. 2 is a graph plotting the relative volume activity of a catalyst as a function of residual carbon content of a spent hydroprocessing catalyst after a carbon removal step.

Claims (49)

A method for recovering the catalytic activity of a used hydroprocessing catalyst,
Providing the spent hydroprocessing catalyst having a first carbon concentration greater than about 3 wt%;
To provide a carbon reduction catalyst having a second carbon concentration in the range of about 0.5 wt% to about 2.5 wt%, by reducing the carbon concentration on the spent hydroprocessing catalyst. The second carbon by contacting the spent hydroprocessing catalyst with an oxygen-containing gas containing oxygen under carbon combustion conditions and adjusting the amount of carbon removed from the spent hydroprocessing catalyst. Providing said carbon-reducing catalyst having a concentration; and treating said carbon-reducing catalyst with a chelating agent, thereby providing a reactivation catalyst. The processing steps are:
Incorporating the chelating agent into the carbon reducing catalyst by contacting the carbon reducing catalyst with a solution comprising the chelating agent and a solvent;
The carbon-reducing catalyst incorporating the solution therein is aged for an aging time, thereby providing an aging catalyst (where the aging time imparts a recovered catalytic activity to the carbon-reducing catalyst. And drying the aging catalyst to remove a portion of the solvent from the aging catalyst, thereby providing a dry aging catalyst, thus providing the reactivation catalyst with The method of claim 1, comprising providing. The processing steps further include:
The method of claim 2, comprising sulfur treating the dry aging catalyst, thus providing the reactivation catalyst.   4. The method of claim 3, wherein the chelating agent is selected from the group consisting of aminocarboxylic acids, polyamines, amino alcohols, oximes, and polyethyleneimines.   The method of claim 4, wherein the solvent of the solution is water.   6. The method of claim 5, wherein the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA).   The method of claim 6, wherein the aging time exceeds about 10 hours.   The method of claim 7, wherein the first carbon concentration is in the range of 5 wt% to 25 wt%, and the second carbon concentration is in the range of 0.75 wt% to 1.75 wt%. .   9. The method of claim 8, wherein greater than about 50% of the chelating agent incorporated in the carbon reduction catalyst remains in the dry aging catalyst.   The chelating agent is diethylenetriaminepentaacetic acid (DTPA); the aging time exceeds 20 hours; the first carbon concentration is in the range of 6 wt% to 20 wt%; in the carbon reducing catalyst The process according to claim 9, wherein more than 75 wt% of the chelating agent incorporated is present in the dry aging catalyst. The processing steps are:
Incorporating the chelator into the carbon-reduced spent catalyst by contacting the carbon-reduced spent catalyst with a solution comprising the chelator and a solvent;
The carbon-reducing catalyst incorporating the solution therein is aged for an aging time, thereby providing an aging catalyst (where the aging time imparts a recovered catalytic activity to the carbon-reducing catalyst. And d) drying said ripening catalyst to remove a portion of said solvent therefrom and providing said reactivation catalyst.   The method of claim 11, further comprising sulfur treating the aged catalyst from which the portion of the solvent has been removed, thereby providing the reactivated catalyst.   13. The method of claim 12, wherein the chelating agent is selected from the group consisting of aminocarboxylic acids, polyamines, amino alcohols, oximes, and polyethyleneimines.   The method of claim 13, wherein the solvent of the solution is water.   15. The method of claim 14, wherein the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA).   16. The method of claim 15, wherein the aging time exceeds about 10 hours.   15. The method of claim 14, wherein the first carbon concentration is in the range of 5 wt% to 25 wt%, and the second carbon concentration is in the range of 0.75 wt% to 1.75 wt%. .   The chelating agent is diethylenetriaminepentaacetic acid (DTPA); the aging time exceeds 20 hours; the first carbon concentration is in the range of 6 wt% to 20 wt%; and the second carbon 18. A method according to claim 17, wherein the concentration is in the range of 1% to 1.5% by weight.   19. The method of claim 18, wherein less than about 50% by weight of the chelating agent incorporated in the carbon reduced spent catalyst is removed from the aged catalyst during the drying step. Providing a spent high activity hydrotreating catalyst having reduced RVA and a first carbon concentration of deposited carbon, wherein the spent highly active hydrotreating catalyst is highly active hydrotreating under hydrotreating conditions Carbon is obtained from using the treatment catalyst and is deposited thereon, resulting in a first carbon concentration of the deposited carbon.);
Heat treating the spent high activity hydrotreating catalyst by contacting the spent highly active hydrotreating catalyst with an oxygen-containing gas under carbon combustion conditions, thereby having a second carbon concentration. Providing a spent high activity hydrotreating catalyst; and adjusting the second carbon concentration by controlling the carbon combustion conditions and the heat treated spent high activity hydrogen having a maximized regenerated RVA Providing a hydrotreating catalyst.   The highly active hydrotreating catalyst includes a porous support and a catalytically active metal (wherein the highly active hydrotreating catalyst includes the porous support and the catalytically active metal including a volatile compound. Forming an uncalcined catalyst precursor having a volatile component in the range of 0.5 wt% to 25 wt% and sulfur treating the catalyst precursor to provide the highly active hydrotreating catalyst 21.) The method of claim 20.   22. The method of claim 21, further comprising subjecting the heat treated spent high activity hydrotreating catalyst to a chelation, thereby providing a reactivated catalyst having a reactivated RVA.   23. The method of claim 22, wherein the reduced RVA is less than 0.65 and the reactivated RVA is at least 0.8. The chelation treatment is:
Contacting the heat treated spent high activity hydrotreating catalyst with a solution comprising the chelating agent and a solvent and incorporating the chelating agent into the heat treated spent high activity hydrotreating catalyst; and the solution Aging the heat-treated spent high-activity hydrotreating catalyst incorporated therein for the aging time, thereby providing an aging catalyst (where the aging time is restored to the carbon-reducing catalyst) Sufficient to provide the desired catalytic activity, thereby providing the reactivated catalyst.)
24. The method of claim 23, comprising:   25. The method of claim 24, wherein the chelation further comprises drying the aging catalyst to remove a portion of the solvent to provide the reactivation catalyst.   26. The method of claim 25, further comprising sulfur treating the aged catalyst from which the portion of the solvent has been removed to provide the reactivated catalyst.   27. The method of claim 26, wherein the chelator is selected from the group consisting of amino carboxylic acids, polyamines, amino alcohols, oximes, and polyethyleneimines.   28. The method of claim 27, wherein the solvent of the solution is water.   30. The method of claim 28, wherein the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA).   30. The method of claim 29, wherein the aging time exceeds about 10 hours.   31. The method of claim 30, wherein the first carbon concentration is in the range of 5 wt% to 25 wt%, and the second carbon concentration is in the range of 0.75 wt% to 1.75 wt%. .   The chelating agent is diethylenetriaminepentaacetic acid (DTPA); the aging time exceeds 20 hours; the first carbon concentration ranges from 6% to 20% by weight; the second carbon concentration 32. The method of claim 31, wherein is in the range of 1% to 1.5% by weight; and the reduced RVA is less than 0.5; and the reactivated RVA is at least 0.85.   21. The method of claim 20, further comprising treating the heat treated spent high activity hydrotreating catalyst with a chelating agent to provide a reactivation catalyst. The processing steps are:
Contacting the heat treated spent high activity hydrotreating catalyst with a solution comprising a chelating agent and a solvent, and incorporating the chelating agent into the heat treated spent high activity hydrotreating catalyst; and the chelating agent Aging the heat-treated spent high-activity hydrotreating catalyst incorporated therein for the aging time, thereby providing an aging catalyst (where the aging time is restored to the carbon-reducing catalyst) Sufficient to provide the desired catalytic activity.)
34. The method of claim 33, comprising: The processing steps are:
35. The method of claim 34, further comprising drying the aging catalyst and removing a portion of the solvent from the aging catalyst, thereby providing a dry aging catalyst.   36. The method of claim 35, further comprising sulfur treating the aged catalyst from which the portion of the solvent has been removed to provide the reactivation catalyst.   38. The method of claim 36, wherein the chelator is selected from aminocarboxylic acids, polyamines, amino alcohols, oximes, and polyethyleneimines.   38. The method of claim 37, wherein the solvent of the solution is water.   40. The method of claim 38, wherein the chelator is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA).   40. The method of claim 39, wherein the aging time exceeds about 10 hours.   41. The method of claim 40, wherein the first carbon concentration is in the range of 5 wt% to 25 wt%, and the second carbon concentration is in the range of 0.75 wt% to 1.75 wt%. .   The chelating agent is diethylenetriaminepentaacetic acid (DTPA); the aging time exceeds 20 hours; the first carbon concentration ranges from 6% to 20% by weight; the second carbon concentration 42. The method of claim 41, wherein is in the range of 1% to 1.5% by weight; and the reduced RVA is less than 0.5. A method for optimally reactivating a spent hydrotreating catalyst having a spent hydrotreated carbon concentration, comprising:
The spent hydrotreating catalyst is heat treated by contacting the spent hydrotreated catalyst with an oxygen-containing gas under carbon combustion conditions, thereby reducing a reduced carbon concentration below the spent hydrotreated carbon concentration. Providing a heat treated spent hydrotreating catalyst comprising:
A catalyst having a recovered RVA greater than about 0.85 after adjusting the reduced carbon concentration by controlling the carbon combustion conditions and chelating the heat treated spent hydroprocessing catalyst. Providing the reduced carbon concentration in a range to provide; and
Thereafter, the method comprising: subjecting the heat treated spent hydrotreating catalyst having the reduced carbon concentration to the chelation, thereby providing the reactivation catalyst.   44. The method of claim 43, wherein the spent hydrotreated carbon concentration is greater than about 3.5% by weight.   45. The method of claim 44, wherein the reduced carbon concentration is in the range of 0.5 wt% to 2.5 wt%.   46. The method of claim 45, wherein the RVA of the reactivation catalyst is greater than 0.85.   47. A catalyst with recovered activity made by the method of claims 1-46.   Including a catalyst having recovered activity, including a spent hydroprocessing catalyst, on which a deactivating concentration of carbon is deposited (wherein the deactivating concentration of carbon comprises a portion of an oxygen-containing gas); Heat treating the spent hydrotreating catalyst in the presence yields an optimized concentration of carbon, after which the spent hydrotreated catalyst thus heat treated is already chelated. A composition).   47. A hydroprocessing method comprising contacting a hydrocarbon feedstock with a catalyst made by any one of the methods of claims 1-46 under hydroprocessing conditions.

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